EP3235785A1 - Method and assembly for the production of synthesis gas by catalytic steam reforming of a hydrocarbonaceous feed gas - Google Patents

Method and assembly for the production of synthesis gas by catalytic steam reforming of a hydrocarbonaceous feed gas Download PDF

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Publication number
EP3235785A1
EP3235785A1 EP16400012.7A EP16400012A EP3235785A1 EP 3235785 A1 EP3235785 A1 EP 3235785A1 EP 16400012 A EP16400012 A EP 16400012A EP 3235785 A1 EP3235785 A1 EP 3235785A1
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EP
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Prior art keywords
steam
gas
production
boiler
pure
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EP16400012.7A
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German (de)
French (fr)
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EP3235785B1 (en
Inventor
Jean-Philippe Tadiello
Taekyu Kang
Thomas Wenz
Chen YUE
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Application filed by LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude filed Critical LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Priority to EP16400012.7A priority Critical patent/EP3235785B1/en
Priority to PL16400012T priority patent/PL3235785T3/en
Priority to ES16400012T priority patent/ES2709688T3/en
Priority to DE102016114120.8A priority patent/DE102016114120A1/en
Priority to CA3021436A priority patent/CA3021436C/en
Priority to MX2018012775A priority patent/MX368256B/en
Priority to PCT/EP2017/025088 priority patent/WO2017182140A1/en
Priority to KR1020187031879A priority patent/KR102354065B1/en
Priority to EA201892279A priority patent/EA038145B1/en
Priority to US16/093,875 priority patent/US10894714B2/en
Priority to SG11201809103PA priority patent/SG11201809103PA/en
Priority to CN201720483534.3U priority patent/CN207891043U/en
Priority to CN201710307263.0A priority patent/CN107364831B/en
Publication of EP3235785A1 publication Critical patent/EP3235785A1/en
Priority to SA518400272A priority patent/SA518400272B1/en
Application granted granted Critical
Publication of EP3235785B1 publication Critical patent/EP3235785B1/en
Priority to US17/122,767 priority patent/US12024428B2/en
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/384—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts the catalyst being continuously externally heated
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0006—Controlling or regulating processes
    • B01J19/0013—Controlling the temperature of the process
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00157—Controlling the temperature by means of a burner
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0495—Composition of the impurity the impurity being water
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C01B2203/0816—Heating by flames
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0872—Methods of cooling
    • C01B2203/0888—Methods of cooling by evaporation of a fluid
    • C01B2203/0894—Generation of steam
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/16—Controlling the process
    • C01B2203/1628—Controlling the pressure
    • C01B2203/1638—Adjusting the pressure

Definitions

  • the invention relates to a method for producing a synthesis gas consisting mainly of hydrogen and carbon monoxide by catalytic steam reforming of a hydrocarbon-containing feed gas, wherein the heat required for the course of the chemical reforming reactions is generated by burners to produce a flue gas and wherein, using the in the synthesis and Heat contained in the flue gas is a pure steam from boiler feed water and a process steam from process condensate is generated.
  • the invention further relates to a system for carrying out this method.
  • process steam The water vapor used together with the hydrocarbon-containing feed gas is called process steam. It is obtained by re-evaporating the condensate formed and separated from the synthesis gas as it is cooled. The heat content of the synthesis and the flue gas, however, exceeds the amount of heat required to produce the process steam. To make good use of this surplus heat, it is used to generate so-called export steam, which is mainly used outside the SMR process. In order not to burden the export steam with impurities from the SMR process, fresh boiler feed water is used to produce it. Part of the export steam is used to compensate for blowdown losses in process steam generation.
  • the object of the invention is to provide a method and a plant in which the heat transfer from the synthesis and the flue gas for generating the vapors is alternatively solved.
  • a preferred embodiment of the method is characterized in that the respective pressures of the part of the pure steam, which is used as a heat transfer medium for the production of process steam, and the part which is discharged as export steam from the process, be set independently.
  • An often demanded by procedural extra consumer pressure for the export steam is 52 bar.
  • this pressure is not optimal for the process internal use of the steam as the heat transfer medium.
  • This embodiment makes it possible to reduce the pressure for this internal use to, for example, 39 bar. By this pressure reduction, the enthalpy of condensation of the steam is increased by 5.8%, which leads to a reduction in the amount of pure steam required for the generation of process steam.
  • the parts used for process steam generation can be designed for this lower pressure, and thus more cost-effectively.
  • a preferred embodiment of the system according to the invention is characterized in that separate control devices for adjusting and regulating the pressures of the part of the pure steam, which is used as a heat transfer medium for the production of process steam, and the part which is discharged as export steam from the process available are.
  • the vapor pressure can be set separately to the requirements of the export steam generator and also the internal process steam generation.
  • a further preferred embodiment of the system according to the invention is characterized in that the steam boiler is equipped for generating process steam with an internal plate heat exchanger.
  • Plate heat exchangers provide so much heat exchanger surface area based on the outer dimensions of the heat exchanger that the heat exchanger can be integrated in the steam boiler and an external heat exchanger can thus be dispensed with.
  • a further preferred embodiment of the system according to the invention is characterized in that the equipment parts coming into contact with process condensate and process steam are made of stainless steel.
  • This construction makes it possible Contaminants, such as CO and CO 2 , to leave in the process condensate, ie the environment is not burdened by a degassing of the process condensate and these components are fed back to the reforming process via the process steam.
  • Contaminants such as CO and CO 2
  • the flow diagram shows an exemplary embodiment of the system 1 according to the invention, which in this example for the production of hydrogen from a hydrocarbon-containing feed gas, such as. B. natural gas and steam is used. Shown are only the understanding of the invention essential parts of the system or the process.
  • the feed gas consisting of natural gas 3 and process steam 4 is converted into synthesis gas 5 consisting mainly of carbon monoxide and hydrogen.
  • the SMR reformer 2 is heated with burners 6, of which only one is shown here, which are operated with air 7 and fuel gas 8 be, with a flue gas 9 is generated.
  • burners 6, of which only one is shown here which are operated with air 7 and fuel gas 8 be, with a flue gas 9 is generated.
  • the synthesis gas 5 and in the flue gas 9 they are used as a heat transfer medium for heating the steam boiler 10, by means of the heat exchangers 10a and 10b, and the synthesis gas 5 in addition to heat the natural gas 3, by means of heat exchanger 20, and the degassing 11, by means of the heat exchanger 11a used.
  • boiler feed water 12 is thermally degassed, the expelled gas 21 is discharged from the system.
  • the degasified and heated boiler feed water is added via line 13 into the steam boiler 10, where it is evaporated to pure steam 14.
  • Part of the clean steam 14 is discharged from the process as the export steam 14a, the other part 14b is used, as heating steam, for heating the steam boiler 17 equipped with the internal plate heat exchanger 17a.
  • the resulting in heat exchanger 17a condensate is returned via line 22 into the degassing 11.
  • valves 23 a and 23 b respectively, the pressures of the vapors 14 a and b are set.
  • the flue gas 9 is, after the heat exchange with boiler feed water in heat exchanger 10b, discharged from the process for further treatment.
  • aqueous condensate 16 is separated and introduced into steam boiler 17. There it is, by means of the heat exchanger 17a, evaporated to process steam 4, wherein a partial stream of the pure steam 14 as heating steam 14a, heat transfer medium, used and then introduced into the degassing 11.
  • the synthesis gas 5 is treated in the pressure swing adsorption system 18, wherein the hydrogen portion 19 is separated from the synthesis gas and discharged for further treatment from the plant or the process.
  • the remaining after the hydrogen separation residual gas 8 is fed as fuel gas 8 to the burners 6 of the SMR reformer 2.
  • the invention provides an alternative method and plant for generating synthesis gas by steam reforming a hydrocarbon-containing gas.
  • the system for generating process steam was redesigned, which results in energy and design advantages.
  • the invention is therefore industrially applicable.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

Verfahren und Anlage zur Erzeugung eines hauptsächlich aus Wasserstoff und Kohlenmonoxid bestehenden Synthesegases durch katalytische Dampfreformierung eines kohlenwasserstoffhaltigen Einsatzgases, wobei die für den Ablauf der chemischen Reformierungsreaktionen erforderliche Wärme von Brennem unter Erzeugung eines Rauchgases erzeugt wird und wobei, unter Nutzung der im Synthese- und im Rauchgas enthaltenen Wärme ein Reindampf aus Kesselspeisewasser und ein Prozessdampf aus Prozesskondensat erzeugt wird, wobei für die Erzeugung des Reindampfs Synthese- und Rauchgas und für die Erzeugung des Prozessdampfs ein Teil des Reindampfs als Wärmeträgermedium verwendet wird und der restliche Teil des Reindampfs als Exportdampf aus dem Verfahren ausgeleitet wird.A process and plant for producing a synthesis gas mainly consisting of hydrogen and carbon monoxide by catalytic steam reforming of a hydrocarbon-containing feed gas, wherein the heat required for the course of the chemical reforming reactions of Brennem is generated to produce a flue gas and wherein, using the synthesis and the flue gas a pure steam from boiler feed water and a process steam from process condensate is generated, wherein for the production of pure steam synthesis and flue gas and for the production of process steam, a portion of the pure steam is used as the heat transfer medium and the remaining part of the pure steam discharged as export steam from the process becomes.

Description

Gebiet der ErfindungField of the invention

Die Erfindung betrifft ein Verfahren zur Erzeugung eines hauptsächlich aus Wasserstoff und Kohlenmonoxid bestehenden Synthesegases durch katalytische Dampfreformierung eines kohlenwasserstoffhaltigen Einsatzgases, wobei die für den Ablauf der chemischen Reformierungsreaktionen erforderliche Wärme von Brennern unter Erzeugung eines Rauchgases erzeugt wird und wobei, unter Nutzung der im Synthese- und im Rauchgas enthaltenen Wärme ein Reindampf aus Kesselspeisewasser und ein Prozessdampf aus Prozesskondensat erzeugt wird.The invention relates to a method for producing a synthesis gas consisting mainly of hydrogen and carbon monoxide by catalytic steam reforming of a hydrocarbon-containing feed gas, wherein the heat required for the course of the chemical reforming reactions is generated by burners to produce a flue gas and wherein, using the in the synthesis and Heat contained in the flue gas is a pure steam from boiler feed water and a process steam from process condensate is generated.

Die Erfindung betrifft weiterhin eine Anlage zur Durchführung dieses Verfahrens.The invention further relates to a system for carrying out this method.

Stand der TechnikState of the art

Derartige Verfahren und Anlagen sind bekannt. Das diesen zugrunde liegende Verfahren zur katalytischer Dampfreformierung eines kohlenwasserstoffhaltigen Einsatzgases ist beispielsweise in Ullmanns Encyclopedia of Industrial Chemistry, Sixth Edition, Vol. 15, Gas Production, Chapter 2. beschrieben ist. Die Einsatzgase, ein kohlenwasserstoffhaltiges Gas, wie z. B. Erdgas und Wasserdampf werden dabei bei erhöhtem Druck, z. B. bei 20 bis 35 bar, und hoher Temperatur, z. B. 800 bis 950 °C, durch von außen beheizte, mit Katalysator gefüllte Reaktorrohre geleitet. Dabei werden die Ein-AIR LIQUIDE-Aktenzeichen 2016P00139 satzgase in wasserstoff- und kohlenmonoxidreiches Synthesegas umgewandelt. Ein derartiger Röhrenreaktor wird häufig als SMR und das Verfahren als SMR-Verfahren bezeichnet, abgekürzt für Steam-Methane-Reformer. Für die Abtrennung des Wasserstoffanteils aus dem Synthesegas wird häufig das Pressure-Swing-Adsorption-Verfahren angewandt, das im selben Ullmann-Band, im Kapitel 5.5.3 beschrieben ist.Such methods and systems are known. The underlying process for the catalytic steam reforming of a hydrocarbon-containing feed gas is described for example in Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, Vol. 15, Gas Production, Chapter 2. The feed gases, a hydrocarbon-containing gas, such as. B. natural gas and water vapor are at elevated pressure, eg. B. at 20 to 35 bar, and high temperature, for. B. 800 to 950 ° C, passed through heated from the outside, filled with catalyst reactor tubes. This will be the one-AIR LIQUIDE file reference 2016P00139 set gases converted into hydrogen and carbon monoxide rich synthesis gas. Such a tube reactor is often referred to as SMR and the process as SMR process, abbreviated to steam methane reformer. For the separation of the hydrogen content from the synthesis gas, the pressure swing adsorption process is frequently used, which is described in the same Ullmann volume, in chapter 5.5.3.

Für die Wirtschaftlichkeit des Verfahrens ist es sehr wichtig, die für die Aufheizung der Einsatzgase und die Durchführung der, in der Summe, endothermen Reformierungsreaktionen aufgewendete Heizenergie möglichst weitgehend zur Dampferzeugung zu verwenden. Der, zusammen mit dem kohlenwasserstoffhaltigen Einsatzgas, eingesetzte Wasserdampf wird als Prozessdampf bezeichnet. Er wird durch Wiederverdampfen des aus dem Synthesegas, bei dessen Abkühlung, gebildeten und abgeschiedenen Kondensats gewonnen. Der Wärmegehalt des Synthese- und des Rauchgases übersteigt allerdings die zum Erzeugen des Prozessdampfs benötigte Wärmemenge. Um diese Überschusswärme sinnvoll zu nutzen, wird sie zur Erzeugung von sogenanntem Exportdampf, der hauptsächlich außerhalb des SMR-Prozesses verwendet wird, genutzt. Um den Exportdampf nicht mit Verunreinigungen aus dem SMR-Prozess zu belasten, wird zu seiner Erzeugung frisches Kesselspeisewasser eingesetzt. Ein Teil des Exportdampfs wird genutzt, um Abschlämmverluste bei der Prozessdampferzeugung auszugleichen.For the economy of the process, it is very important to use as much as possible for steam generation for the heating of the feed gases and the implementation of, in the sum, endothermic reforming reactions heat energy. The water vapor used together with the hydrocarbon-containing feed gas is called process steam. It is obtained by re-evaporating the condensate formed and separated from the synthesis gas as it is cooled. The heat content of the synthesis and the flue gas, however, exceeds the amount of heat required to produce the process steam. To make good use of this surplus heat, it is used to generate so-called export steam, which is mainly used outside the SMR process. In order not to burden the export steam with impurities from the SMR process, fresh boiler feed water is used to produce it. Part of the export steam is used to compensate for blowdown losses in process steam generation.

Die Nutzung der im Synthese- und im Rauchgas enthaltenen Wärme zur Dampferzeugung erfolgt in vielen Fällen, indem ein indirekter Wärmeaustausch zwischen diesen Gasen und dem Prozesskondensat und dem Kesselspeisewasser durchgeführt wird. Die deutsche Patentschrift DE 10 2010 044 939 B3 beschreibt ein derartig ausgeführtes Verfahren.The use of the heat contained in the synthesis and in the flue gas to generate steam is in many cases by an indirect heat exchange between these gases and the process condensate and the boiler feed water is performed. The German patent DE 10 2010 044 939 B3 describes such a method carried out.

Die Aufgabe der Erfindung besteht darin, ein Verfahren und eine Anlage zur Verfügung zu stellen, in der die Wärmeübertragung vom Synthese- und vom Rauchgas zur Erzeugung der der Dämpfe alternativ gelöst wird.The object of the invention is to provide a method and a plant in which the heat transfer from the synthesis and the flue gas for generating the vapors is alternatively solved.

Beschreibung der ErfindungDescription of the invention

Die Aufgabe wird durch das Verfahren gemäß Anspruch 1 und eine erfindungsgemäße Anlage mit den Merkmalen des Anspruchs 3 gelöst.The object is achieved by the method according to claim 1 and a system according to the invention with the features of claim 3.

Erfindungsgemäßes Verfahren:Inventive method:

Verfahren zur Erzeugung eines hauptsächlich aus Wasserstoff und Kohlenmonoxid bestehenden Synthesegases durch katalytische Dampfreformierung eines kohlenwasserstoffhaltigen Einsatzgases, wobei die für den Ablauf der chemischen Reformierungsreaktionen erforderliche Wärme von Brennern unter Erzeugung eines Rauchgases erzeugt wird und wobei, unter Nutzung der im Synthesegas und im Rauchgas enthaltenen Wärme, ein Reindampf aus Kesselspeisewasser und ein Prozessdampf aus Prozesskondensat erzeugt wird, dadurch gekennzeichnet, dass für die Erzeugung des Reindampfs Synthesegas und Rauchgas und für die Erzeugung des Prozessdampfs ein Teil des Reindampfs als Wärmeträgermedium verwendet wird und der restliche Teil des Reindampfs als Exportdampf aus dem Verfahren ausgeleitet wird.A process for producing a synthesis gas mainly composed of hydrogen and carbon monoxide by catalytic steam reforming of a hydrocarbon-containing feed gas, wherein the heat required for the course of the chemical reforming reactions is generated by burners to produce a flue gas and wherein, using the heat contained in the synthesis gas and in the flue gas, a pure steam from boiler feed water and a process steam from process condensate is generated, characterized in that for the production of pure steam synthesis gas and flue gas and for the production of process steam, a portion of the pure steam is used as the heat transfer medium and the remaining part of the pure steam discharged as export steam from the process becomes.

Eine bevorzugte Ausgestaltung des Verfahrens ist dadurch gekennzeichnet, dass die jeweiligen Drücke des Teils des Reindampfs, der als Wärmeträgermedium für die Erzeugung von Prozessdampf verwendet wird, und des Teils, der als Exportdampf aus dem Verfahren ausgeleitet wird, unabhängig voneinander eingestellt werden. Ein häufig vom verfahrensextemen Verbraucher geforderter Druck für den Exportdampf beträgt 52 bar. Dieser Druck ist aber für die verfahrensinterne Verwendung des Dampfs als Wärmeträgermedium nicht optimal. Diese Ausgestaltung ermöglicht es, den Druck für diese interne Nutzung auf beispielsweise 39 bar zu senken. Durch diese Druckabsenkung wird die Kondensationsenthalpie des Dampfs um 5,8% gesteigert, was zu einer Senkung der für die Erzeugung von Prozessdampf benötigten Menge an Reindampf führt. Außerdem können die für die Prozessdampferzeugung verwendeten Teile auf diesen geringeren Druck, und damit kostengünstiger, ausgelegt werden.A preferred embodiment of the method is characterized in that the respective pressures of the part of the pure steam, which is used as a heat transfer medium for the production of process steam, and the part which is discharged as export steam from the process, be set independently. An often demanded by procedural extra consumer pressure for the export steam is 52 bar. However, this pressure is not optimal for the process internal use of the steam as the heat transfer medium. This embodiment makes it possible to reduce the pressure for this internal use to, for example, 39 bar. By this pressure reduction, the enthalpy of condensation of the steam is increased by 5.8%, which leads to a reduction in the amount of pure steam required for the generation of process steam. In addition, the parts used for process steam generation can be designed for this lower pressure, and thus more cost-effectively.

Erfindungsgemäße Anlage:Inventive plant:

Anlage zur Durchführung des erfindungsgemäßen Verfahrens, umfassend:

  • Mindestens einen Röhrenofen zur Durchführung der katalytischen Dampfreformierung,
  • Einen Kessel zur thermischen Entgasung von Kesselspeisewasser,
  • Einen Dampfkessel zur Erzeugung von Reindampf aus Kesselspeisewasser,
  • Jeweils mindestens einen Wärmetauscher für die Erwärmung und Verdampfung des Kesselspeisewassers durch Synthesegas und durch Rauchgas,
  • Mindestens einen Apparat zur mechanischen Abtrennung von Kondensat aus dem Synthesegas,
  • Einen Dampfkessel zur Erzeugung von Prozessdampf, ausgestattet mit einem Wärmetauscher geeignet zur Verwendung von Reindampf als Wärmeträgermedium.
Plant for carrying out the process according to the invention, comprising:
  • At least one tube furnace for carrying out the catalytic steam reforming,
  • A boiler for the thermal degassing of boiler feed water,
  • A steam boiler for the production of pure steam from boiler feed water,
  • At least one heat exchanger for the heating and evaporation of the boiler feed water by synthesis gas and by flue gas,
  • At least one apparatus for the mechanical separation of condensate from the synthesis gas,
  • A steam boiler for the production of process steam, equipped with a heat exchanger suitable for the use of pure steam as the heat transfer medium.

Eine bevorzugte Ausgestaltung der erfindungsgemäßen Anlage ist dadurch gekennzeichnet, dass separate Regelungsvorrichtungen für die Einstellung und Regelung der Drücke des Teils des Reindampfs, der als Wärmeträgermedium für die Erzeugung von Prozessdampf verwendet wird, und des Teils, der als Exportdampf aus dem Verfahren ausgeleitet wird, vorhanden sind. Durch diese Ausstattung kann der Dampfdruck auf die Anforderungen des Exportdampfabnehmers und auch der internen Prozessdampferzeugung separat eingestellt werden.A preferred embodiment of the system according to the invention is characterized in that separate control devices for adjusting and regulating the pressures of the part of the pure steam, which is used as a heat transfer medium for the production of process steam, and the part which is discharged as export steam from the process available are. Through this equipment, the vapor pressure can be set separately to the requirements of the export steam generator and also the internal process steam generation.

Eine weitere bevorzugte Ausgestaltung der erfindungsgemäßen Anlage ist dadurch gekennzeichnet, dass der Dampfkessel zur Erzeugung von Prozessdampf mit einem innenliegenden Plattenwärmetauscher ausgestattet ist. Plattenwärmetauscher stellen so viel Wärmetauscherfläche bezogen auf die Außenabmessungen des Wärmetauschers zur Verfügung, dass der Wärmetauscher im Dampfkessel integriert werden und ein außenliegender Wärmetauscher somit entfallen kann. Durch diese Bauweise wird der Platzbedarf für die Anlagenteile der Prozessdampferzeugung verringert.A further preferred embodiment of the system according to the invention is characterized in that the steam boiler is equipped for generating process steam with an internal plate heat exchanger. Plate heat exchangers provide so much heat exchanger surface area based on the outer dimensions of the heat exchanger that the heat exchanger can be integrated in the steam boiler and an external heat exchanger can thus be dispensed with. By this construction, the space required for the plant parts of the process steam generation is reduced.

Eine weitere bevorzugte Ausgestaltung der erfindungsgemäßen Anlage ist dadurch gekennzeichnet, dass die mit Prozesskondensat und Prozessdampf in Berührung kommenden Anlagenteile aus rostfreiem Stahl bestehen. Durch diese Bauweise ist es möglich, Verunreinigungen, wie CO und CO2, im Prozesskondensat zu belassen, d.h. die Umwelt wird nicht durch eine Entgasung des Prozesskondensats belastet und diese Bestandteile werden, über den Prozessdampf, dem Reformierungsprozess wieder zugeführt. Durch die Verwendung von Edelstahl kann auch die Zugabe von Chemikalien zur Bindung von Sauerstoff und zur pH-Einstellung unterbleiben.A further preferred embodiment of the system according to the invention is characterized in that the equipment parts coming into contact with process condensate and process steam are made of stainless steel. This construction makes it possible Contaminants, such as CO and CO 2 , to leave in the process condensate, ie the environment is not burdened by a degassing of the process condensate and these components are fed back to the reforming process via the process steam. The use of stainless steel can also eliminate the addition of chemicals for oxygen binding and pH adjustment.

Ausführungsbeispielembodiment

Weitere Merkmale, Vorteile und Anwendungsmöglichkeiten der Erfindung ergeben sich auch aus der nachfolgenden Beschreibung eines Ausführungs- und Zahlenbeispiels und der Zeichnung. Dabei bilden alle beschriebenen und/oder bildlich dargestellten Merkmale für sich oder in beliebiger Kombination den Gegenstand der Erfindung, unabhängig von ihrer Zusammenfassung in den Ansprüchen oder deren Rückbeziehung.Other features, advantages and applications of the invention will become apparent from the following description of an embodiment and numerical example and the drawings. All described and / or illustrated features alone or in any combination form the subject matter of the invention, regardless of their combination in the claims or their dependency.

Das erfindungsgemäße Verfahren soll im Folgenden anhand der Zeichnung Fig. 1 erläutert werden. Dabei zeigt:

Fig. 1
ein Fließbild einer beispielhaften Ausführung der erfindungsgemäßen Anlage
The inventive method will be described below with reference to the drawing Fig. 1 be explained. Showing:
Fig. 1
a flow diagram of an exemplary embodiment of the system according to the invention

Fig.1:Fig.1:

Das Fließbild zeigt eine beispielhafte Ausführung der erfindungsgemäßen Anlage 1, die in diesem Beispiel zur Erzeugung von Wasserstoff aus einem kohlenwasserstoffhaltigen Einsatzgas, wie z. B. Erdgas und Wasserdampf dient. Dargestellt sind nur die zum Verständnis der Erfindung wesentlichen Teile der Anlage bzw. des Verfahrens.The flow diagram shows an exemplary embodiment of the system 1 according to the invention, which in this example for the production of hydrogen from a hydrocarbon-containing feed gas, such as. B. natural gas and steam is used. Shown are only the understanding of the invention essential parts of the system or the process.

In dem als Röhrenofen ausgeführten SMR-Reformer 2 wird das aus Erdgas 3 und Prozessdampf 4 bestehende Einsatzgas in hauptsächlich aus Kohlenmonoxid und Wasserstoff bestehendes Synthesegas 5 umgewandelt. Der SMR-Reformer 2 wird mit Brennern 6, von denen hier nur einer dargestellt ist, beheizt, die mit Luft 7 und Brenngas 8 betrieben werden, wobei ein Rauchgas 9 erzeugt wird. Um die im Synthesegas 5 und im Rauchgas 9 enthaltene Wärme zu nutzen, werden diese als Wärmeträgermedium zur Beheizung des Dampfkessels 10, mittels der Wärmetauscher 10a und 10b, und das Synthesegas 5 zusätzlich auch zur Beheizung des Erdgases 3, mittels Wärmetauscher 20, und des Entgasungskessels 11, mittels des Wärmetauschers 11a, verwendet. Im Entgasungskessel 11 wird Kesselspeisewasser 12 thermisch entgast, das ausgetriebene Gas 21 wird aus der Anlage ausgeleitet. Das entgaste und erwärmte Kesselspeisewasser wird über Leitung 13 in den Dampfkessel 10 gegeben, in dem es zu Reindampf 14 verdampft wird. Ein Teil des Reindampfs 14 wird als Exportdampf 14a aus dem Verfahren bzw. der Anlage ausgeleitet, der andere Teil 14b, wird, als Heizdampf, zur Beheizung des Dampfkessels 17 verwendet, der mit dem innenliegenden Plattenwärmetauscher 17a ausgestattet ist. Das in Wärmetauscher 17a entstandene Kondensat wird über Leitung 22 in den Entgasungskessel 11 zurückgeführt.In the SMR reformer 2 designed as a tube furnace, the feed gas consisting of natural gas 3 and process steam 4 is converted into synthesis gas 5 consisting mainly of carbon monoxide and hydrogen. The SMR reformer 2 is heated with burners 6, of which only one is shown here, which are operated with air 7 and fuel gas 8 be, with a flue gas 9 is generated. To use the heat contained in the synthesis gas 5 and in the flue gas 9, they are used as a heat transfer medium for heating the steam boiler 10, by means of the heat exchangers 10a and 10b, and the synthesis gas 5 in addition to heat the natural gas 3, by means of heat exchanger 20, and the degassing 11, by means of the heat exchanger 11a used. In the degassing 11 boiler feed water 12 is thermally degassed, the expelled gas 21 is discharged from the system. The degasified and heated boiler feed water is added via line 13 into the steam boiler 10, where it is evaporated to pure steam 14. Part of the clean steam 14 is discharged from the process as the export steam 14a, the other part 14b is used, as heating steam, for heating the steam boiler 17 equipped with the internal plate heat exchanger 17a. The resulting in heat exchanger 17a condensate is returned via line 22 into the degassing 11.

Mit den Ventilen 23 a und 23 b werden jeweils die Drücke der Dämpfe 14 a und b eingestellt.With the valves 23 a and 23 b, respectively, the pressures of the vapors 14 a and b are set.

Das Rauchgas 9 wird, nach dem Wärmeaustausch mit Kesselspeisewasser in Wärmetauscher 10b, zur weiteren Behandlung aus dem Verfahren ausgeleitet.The flue gas 9 is, after the heat exchange with boiler feed water in heat exchanger 10b, discharged from the process for further treatment.

In Kondensatabscheider 15 wird im Synthesegas gebildetes wässriges Kondensat 16 abgetrennt und in Dampfkessel 17 eingeleitet. Dort wird es, mittels des Wärmetauschers 17a, zu Prozessdampf 4 verdampft, wobei ein Teilstrom des Reindampfs 14 als Heizdampf 14a, Wärmeträgermedium, verwendet und anschließend in den Entgasungskessel 11 eingeführt wird. Nach der Kondensatabscheidung wird das Synthesegas 5 in der pressure-swing-adsorption-Anlage 18 behandelt, wobei der Wasserstoffanteil 19 aus dem Synthesegas abgetrennt und zur weiteren Behandlung aus der Anlage bzw. dem Verfahren ausgeleitet wird. Das nach der Wasserstoffabtrennung verbleibende Restgas 8 wird als Brenngas 8 den Brennern 6 des SMR-Reformers 2 zugeleitet.In condensate 15 formed in the synthesis gas aqueous condensate 16 is separated and introduced into steam boiler 17. There it is, by means of the heat exchanger 17a, evaporated to process steam 4, wherein a partial stream of the pure steam 14 as heating steam 14a, heat transfer medium, used and then introduced into the degassing 11. After the condensate separation, the synthesis gas 5 is treated in the pressure swing adsorption system 18, wherein the hydrogen portion 19 is separated from the synthesis gas and discharged for further treatment from the plant or the process. The remaining after the hydrogen separation residual gas 8 is fed as fuel gas 8 to the burners 6 of the SMR reformer 2.

Gewerbliche AnwendbarkeitIndustrial Applicability

Die Erfindung stellt ein alternatives Verfahren und eine alternative Anlage zur Erzeugung von Synthesegas durch Dampfreformierung eines kohlenwasserstoffhaltigen Gases zur Verfügung. Dabei wurde das System zur Erzeugung von Prozessdampf neu gestaltet, wodurch energetische und konstruktive Vorteile erzielt werden. Die Erfindung ist daher gewerblich anwendbar.The invention provides an alternative method and plant for generating synthesis gas by steam reforming a hydrocarbon-containing gas. In the process, the system for generating process steam was redesigned, which results in energy and design advantages. The invention is therefore industrially applicable.

BezugszeichenlisteLIST OF REFERENCE NUMBERS

11
Erfindungsgemäße AnlageInventive plant
22
SMR-ReformerSMR reformer
33
Erdgasstromnatural gas stream
44
Prozessdampfprocess steam
55
Synthesegassynthesis gas
66
Brennerburner
77
Luft zur VerbrennungAir for combustion
88th
Rest-/BrenngasResidual / fuel gas
99
Rauchgasflue gas
1010
Dampfkessel für Exportdampf, mit Wärmetauschern 10a, bSteam boiler for export steam, with heat exchangers 10a, b
1111
Entgasuhgskessel mit Wärmetauscher 11aDegassing boiler with heat exchanger 11a
1212
Kesselspeisewasser, frischBoiler feed water, fresh
1313
Kesselspeisewasser, entgastBoiler feed water, degassed
1414
Reindampfclean steam
14a14a
Exportdampfexport steam
14b14b
Heizdampfheating steam
1515
Kondensatabscheidercondensate
1616
Kondensatcondensate
1717
Dampfkessel für Prozessdampf, mit Wärmetauscher 17aSteam boiler for process steam, with heat exchanger 17a
1818
Pressure-swing-adsorption AnlagePressure swing adsorption plant
1919
Wasserstoffhydrogen
2020
Wärmetauscherheat exchangers
2121
Gas, aus Kesselspeisewasser ausgetriebenGas expelled from boiler feed water
2222
Leitung zur KondensatrückführungLine for condensate return
2323
a, b Ventil zur Regelung des Dampfdrucksa, b Valve for controlling the vapor pressure

Claims (6)

Verfahren zur Erzeugung eines hauptsächlich aus Wasserstoff und Kohlenmonoxid bestehenden Synthesegases durch katalytische Dampfreformierung eines kohlenwasserstoffhaltigen Einsatzgases, wobei die für den Ablauf der chemischen Reformierungsreaktionen erforderliche Wärme von Brennern unter Erzeugung eines Rauchgases erzeugt wird und wobei, unter Nutzung der im Synthesegas und im Rauchgas enthaltenen Wärme, ein Reindampf aus Kesselspeisewasser und ein Prozessdampf aus Prozesskondensat erzeugt wird, dadurch gekennzeichnet, dass für die Erzeugung des Reindampfs Synthesegas und Rauchgas und für die Erzeugung des Prozessdampfs ein Teil des Reindampfs als Wärmeträgermedium verwendet wird und der restliche Teil des Reindampfs als Exportdampf aus dem Verfahren ausgeleitet wird.A process for producing a synthesis gas mainly composed of hydrogen and carbon monoxide by catalytic steam reforming of a hydrocarbon-containing feed gas, wherein the heat required for the course of the chemical reforming reactions is generated by burners to produce a flue gas and wherein, using the heat contained in the synthesis gas and in the flue gas, a pure steam from boiler feed water and a process steam from process condensate is generated, characterized in that for the production of pure steam synthesis gas and flue gas and for the production of process steam, a portion of the pure steam is used as the heat transfer medium and the remaining part of the pure steam discharged as export steam from the process becomes. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, dass die jeweiligen Drücke des Teils des Reindampfs, der als Wärmeträgermedium für die Erzeugung von Prozessdampf verwendet wird, und des Teils, der als Exportdampf aus dem Verfahren ausgeleitet wird, unabhängig voneinander eingestellt werden.A method according to claim 1, characterized in that the respective pressures of the part of the pure steam, which is used as a heat transfer medium for the production of process steam, and the part, which is discharged as export steam from the process, are set independently. Anlage zur Durchführung des Verfahrens gemäß Anspruch 1, umfassend: - Mindestens einen Röhrenofen zur Durchführung der katalytischen Dampfreformierung, - Einen Kessel zur thermischen Entgasung von Kesselspeisewasser, - Einen Dampfkessel zur Erzeugung von Reindampf aus Kesselspeisewasser, - Jeweils mindestens einen Wärmetauscher für die Erwärmung und Verdampfung des Kesselspeisewassers durch Synthesegas und durch Rauchgas, - Mindestens einen Apparat zur mechanischen Abtrennung von Kondensat aus dem Synthesegas, - Einen Dampfkessel zur Erzeugung von Prozessdampf, ausgestattet mit einem Wärmetauscher geeignet zur Verwendung von Reindampf als Wärmeträgermedium. Plant for carrying out the method according to claim 1, comprising: At least one tube furnace for carrying out the catalytic steam reforming, A boiler for the thermal degassing of boiler feed water, A steam boiler for the production of pure steam from boiler feed water, - At least one heat exchanger for the heating and evaporation of the boiler feed water by synthesis gas and by flue gas, At least one apparatus for the mechanical separation of condensate from the synthesis gas, - A steam boiler for the production of process steam, equipped with a heat exchanger suitable for the use of pure steam as the heat transfer medium. Anlage gemäß Anspruch 3, dadurch gekennzeichnet, dass separate Regelungsvorrichtungen für die Einstellung und Regelung der Drücke des Teils des Reindampfs, der als Wärmeträgermedium für die Erzeugung von Prozessdampf verwendet wird, und des Teils, der als Exportdampf aus dem Verfahren ausgeleitet wird, vorhanden sind.Installation according to claim 3, characterized in that separate control devices for adjusting and regulating the pressures of the part of the pure steam, which is used as a heat transfer medium for the generation of process steam, and the part which is discharged as export steam from the process, are present. Anlage gemäß Anspruch 3 oder 4, dadurch gekennzeichnet, dass der Dampfkessel zur Erzeugung von Prozessdampf mit einem innenliegenden Plattenwärmetauscher ausgestattet ist.Plant according to claim 3 or 4, characterized in that the steam boiler is equipped for generating process steam with an internal plate heat exchanger. Anlage gemäß einem der Ansprüche 3 bis 5, dadurch gekennzeichnet, dass die mit Prozesskondensat und Prozessdampf in Berührung kommenden Anlagenteile aus rostfreiem Stahl bestehen.Plant according to one of Claims 3 to 5, characterized in that the plant components which come into contact with the process condensate and process steam are made of stainless steel.
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EP16400012.7A EP3235785B1 (en) 2016-04-22 2016-04-22 Method and assembly for the production of synthesis gas by catalytic steam reforming of a hydrocarbonaceous feed gas
PL16400012T PL3235785T3 (en) 2016-04-22 2016-04-22 Method and assembly for the production of synthesis gas by catalytic steam reforming of a hydrocarbonaceous feed gas
ES16400012T ES2709688T3 (en) 2016-04-22 2016-04-22 Procedure and installation for the production of synthesis gas by steam catalytic reforming of a hydrocarbon-containing feed gas
DE102016114120.8A DE102016114120A1 (en) 2016-04-22 2016-07-29 Process and plant for the production of synthesis gas by means of catalytic steam reforming of a hydrocarbon-containing feed gas
US16/093,875 US10894714B2 (en) 2016-04-22 2017-04-12 Process and plant for the production of synthesis gas by means of catalytic steam reformation of a hydrocarbonaceous feed gas
PCT/EP2017/025088 WO2017182140A1 (en) 2016-04-22 2017-04-12 Process and plant for the production of synthesis gas by means of catalytic steam reformation of a hydrocarbonaceous feed gas
KR1020187031879A KR102354065B1 (en) 2016-04-22 2017-04-12 Synthesis gas production process and equipment by catalytic steam reforming of hydrocarbon feed gas
EA201892279A EA038145B1 (en) 2016-04-22 2017-04-12 Process and plant for the production of synthesis gas by means of catalytic steam reformation of a hydrocarbonaceous feed gas
CA3021436A CA3021436C (en) 2016-04-22 2017-04-12 Process and plant for the production of synthesis gas by means of catalytic steam reformation of a hydrocarbonaceous feed gas
SG11201809103PA SG11201809103PA (en) 2016-04-22 2017-04-12 Process and plant for the production of synthesis gas by means of catalytic steam reformation of a hydrocarbonaceous feed gas
MX2018012775A MX368256B (en) 2016-04-22 2017-04-12 Process and plant for the production of synthesis gas by means of catalytic steam reformation of a hydrocarbonaceous feed gas.
CN201720483534.3U CN207891043U (en) 2016-04-22 2017-04-24 Facility for generating synthesis gas by the catalytic steam reforming of hydrocarbon raw material gas
CN201710307263.0A CN107364831B (en) 2016-04-22 2017-04-24 Method and installation for producing synthesis gas by catalytic steam reforming of a hydrocarbon feed gas
SA518400272A SA518400272B1 (en) 2016-04-22 2018-10-18 Process and Plant for the Production of Synthesis Gas by means of Catalytic Steam Reformation of a Hydrocarbonaceous Feed Gas
US17/122,767 US12024428B2 (en) 2016-04-22 2020-12-15 Process and plant for the production of synthesis gas by means of catalytic steam reformation of a hydrocarbonaceous feed gas

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